Acrylonitrile polymer composition stabilized with metal formaldehyde sulfoxylate, a six membered n-formyl heterocyclic compound, and an inorganic acid, and method of making same



United States Patent ACRYLONITRILE POLYMER COMPOSITION STABILIZED WITH METAL FORMALDE- HYDE'SULFOXYLATE, A SIX MEMBERED N-FORMYL HETEROCYCLIC COMPOUND, AND AN INORGANIC ACID, AND METHOD OF MAKING SAME Richard R. Holmes, Bethesda, Md., and Lloyd T. Jenkins,

Decatur, Ala., assignors to The Chemstrand Corporation, Decatur, Ala., a corporation of Delaware No Drawing. Application May 23, 1956 Serial No. 586,658

21 Claims. c1. 260--32.6)

This invention relates to the stabilization of acrylonitrile polymers and blends thereof. More particularly, it relates to the stabilization of acrylonitrile polymers and blends thereof which have a tendency to develop color upon standing or application of heat.

The term polymer, as employed in the instant description and claims, is intended to include homopoylmers, copolymers, and blends thereof, said polymers containing at least 80 percent by weight of polymerized or copolymerized acrylonitrile in the polymer molecule.

Acrylonitrile polymers containing 80 percent or more of acrylonitrile are generally insoluble in the more common solvents and in those instances where suitable solvents have been found, in order to effect solution, the application of heat is usually necessary. Where heat is employed to effect solutions, from which shaped articles are to be formed, a tan to dark brown color frequently develops in the solutions and therefore is carried over into the product formed therefrom. This color also develops in solutions upon standing for prolonged periods of time.

The mechanism which causes color formation has not been definitely ascertained, although a variety of reasons therefor have been advanced. The presence of metal ions, such as iron, copper and manganese in the solutions may cause the color. The employment of amide compounds as solvents may result in formation of amines when heat is applied and cause color in the compositions. Impurities present in the solvents have also been cited as a cause. tion, it results in compositions and products of undesirable standards and therefore, has been the source of concern, particularly in commercial operations where such types of polymers or copolymers are employed.

Accordingly, it is an object of the present invention to prevent undesirable color formation in acrylonitrile poly mer compositions.

Another object is to minimize color formation'when solutions of the acrylonitrile polymers are permitted to stand for a prolonged period of time or upon application of heat.

It is also an object of the invention to prevent color formation in acrylonitrile polymers at elevated temperatures.

A still further object of the invention is the production of solutions of acrylonitrile polymers and articles produced therefrom having improved color characteristics.

Other objects and advantages will be apparent from a consideration of the description of the invention which follows hereafter.

In general, the objects of the invention are accomplished by dissolving the polymer of acrylonitrile in a suitable solvent therefor and preventing or minimizing color formation by the presence in the solution as an inhibiting Whatever may be the reason for color forma v agent, a combined reagent comprising an organic metal 2,878,203 I Patented Mar. 17,

sulfoxylate, a heterocyclic ring compound and an 'inor ganic acid having an ionization constant greater than 1 10- Among the sulfoxylates which may be employed in practising the instant invention are those having the general formula,

in which R is an alkanol group containing 1 to 3 carbon atoms, an acyl group containing 1 to 3 carbon atoms or an aryl group containing 6 to 8 carbon atoms, n is an integer from 1 to 2, and M is sodium, potassium, zinc, etc. Compounds illustrative of this class are sodium formaldehyde sulfoxylate, zinc formaldehyde sulfoxylate, potassium formaldehyde sulfoxylate, zinc ace'taldehyde sulfoxylate, sodium acetaldehyde sulfoxylate, potassium acetaldehyde sulfoxylate, zinc propionaldehyde sulfoxylate, sodium propionaldehyde sulfoxylate, potassium propionaldehyde sulfoxylate, etc.

Among the heterocyclic ring compounds which may be employed in practising the instant invention are those having the general formula,

CHz-CH: H R/ \N(|J=O CHrCg wherein R is oxygen or NCHO. Compounds illustrative of this class are N-formyl morpholine, Nformyl piperidine, diformyl piperazine, etc. Another excellent heterocyclic ring compound which may be employed in practisingthe instant invention is N-formyl pyrrolidine. Thecomponents of the inhibiting agent may be employed in equal or unequal amounts, any one constituent being present in a range of from 98 to 1 percent in a three component system. The total amount of inhibiting agentmay be employed in a range of about 0.3 to '15 percent, based on the total polymer weight. However, it is preferred that the inhibiting agent of the instant invention be present in a small amount compared to the amount of polymer dissolved. Thus, although the amount is not critical, it is preferred that the inhibiting agent be present in the amount of about 0.3 to 3.0 percent, based on the total weight of the polymer. The inhibiting agent may be added to the solvents before or after the polymer is dissolved therein. The inhibiting agent permits exposure to high temperatures for prolonged standing periods without the development of the objectionable color which usually results in such solutions. The compositions of the instant invention may be prepared in a varying temperature range. For example, the compositions of the instant invention may be prepared by mixing the polymer, a suitable solvent and the inhibiting agent at any temperature or heating the mixture to a temperature up to the boiling point of the solvent.

Among the acids having an ionization constant greater than 1x10- which may be employed in practising the instant invention are sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, etc.

Among the solvents which may be used in practising the instant invention are N,N-dimethylformamide, N,N- dimethylacetamide, aqueous zinc chloride, sulfuric acid, aqueous nitric acid, aqueous sodium thiocyanate, ethylene carbonate, sulfolane, nitromethane, etc.

The polymeric materials, which may be employed in the practice of the present invention, are polyacrylonitrile, copolymers, including binary and ternary polymers contal'ning atleast 8 0 percent by weight of acrylonitrile in the polymer molecule, or a blend comprising polyarylonitrile or copolymers comprising acrylonitrile with from 2 to- 50 percent of another polymeric material, the blend having an overall polymerized acrylonitrile content of at least 80 percent by weight. While the preferred polymers employed in the instant invention are those containingat least 80 percent of acrylonitrile, generally recogriized as the fiber-forming acrylonitrile polymers, it will be understood that the invention is likewise applicable to polymers containing less than 80 percent acrylonitrile and the same stability is realized with the inhibiting agents defined herein. The acrylonitrile polymers containing less than 80 percent acrylonitrile areuseful in forming films, coating compositions, molding operations, lacquers, etc'., in all of which applications the alleviation of undesirable color is extremely important.

.For example, the polymer may be a copolymer of from -80 to 98 percent acrylonitrile and from 2 to 20 percent of another monomer containing the C=C linkage and copolymerizable with acrylonitrile. Suitable monoolefinic monomers include acrylic, alpha-chloroacrylic and methacrylic acids; the acrylates, such as methylmethacrylate, ethylmethacrylate, butylmethacrylate, methoxymethyl methacrylate, beta-chloroethylmethacrylate, and the corresponding esters of acrylic and alpha-chloroacrylic acids; vinyl chloride, vinyl fluoride, vinyl bromide, vinylidene chloride, l-chloro-l-bromoethylene; methacrylonitrile; acrylamide and methacrylamide; alpha-chloroacrylamide, or monoalkyl substitution products thereof; methyl vinyl ketone; vinyl carboxylates, such as vinyl acetate, vinyl chloroacetate, vinyl propionate, and vinyl stearate; N-vinylimides, such as N-vinylphthalimide and N-vinylsuccinimide; methylene malonic esters; itaconic acid and itaconic ester; N-vinylcarbazole; vinyl furane; alkylvinyl esters; vinyl sulfonic acid; ethylene alpha, betadicarboxylic acids or their anhydrides or derivatives, such as diethylcitraconate, diethylmesaconate, styrene, vinyl naphthalene; vinyl-substituted tertiary heterocyclic amines, such as the vinylpyridines and alkyl-substituted vinylpyridines, for example, 2-vinylpyridine, 4-vinylpyridine,

-2-methyl-S-vinylpyridine, etc.; l-vinylimidazole and alkylsubstituted l-vinylimidazoles, such as 2-, 4-, or S-methyll-vinylimidazole, and other C=C containing polymerizable materials.

The polymer may be a ternary interpolymer, for example, products obtained by the interpolymerization of acrylonitrile and two or more of any of the monomers,

other than acrylonitrile, enumerated above. More specifically, and preferably, the ternary polymer comprises acrylonitrile, methacrylonitrile, and 2-vinylpyridine. The

ternary polymers preferably contain from 80 to 97 percent of acrylonitrile, from 1 to 10 percent of a vinyl-,

pyridine or a l-vinylimidazole, and from 1 to 18 percent of another substance, such as methacrylonitrile or vinyl chloride.

The polymer may also be a blend of polyacrylonitrile or of a binary interpolymer of from 80 to 99 percent acrylonitrile and from 1 to 20 percent of at least one other C= containing substance with from 2 to 20 percent of the weight of the blend of'a copolymer of from 10 to 70 ,percent of acrylonitrile and from 30 to 90 percent of at idazone, to give a dyeable blend having an overall vinyl--- substituted tertiary heteroc'yclic amine content of from 2 to 10 percent, based on the weight of the blend;

The polymers, useful in the practiee of the present invention, may be prepared by any conventional polymerization procedures, such as mass polymerization methods, solution polymerization methods, or aqueous emulsion procedures. However, the preferred practice utilizes suspension polymerization wherein the polymer is prepared in finely divided form for immediate use in the fiber fabrication operations. The preferred suspension polymerization may utilize batch procedures, wherein monomers are charged with an aqueous medium containing the necessary catalyst and dispersing agents. A more desirable method involves the semi-continuous procedure in which the polymerization reactor containing the aqueous medium is charged with the desired monomers and the continuousv withdrawal of polymer may also be employed.

The polymerization is catalyzed by means of any watersoluble peroxy compound, for example the potassium, ammonium and other Water-soluble salts of peroxy acids, sodium peroxide, hydrogen peroxide, sodium perborate, the sodium salts of other peroxy acids, and any other water-soluble compound containing a peroxy group (--OO-). A wide variation in the quantity of peroxy compound is possible. For example, from 0.1 to 3.0 percent by weight of the polymerizable monomer may be used. The catalyst may be charged at the outset of the reaction, or it may be added continuously'or in increments throughout the reaction for the purpose of maintaining a more uniform concentration of catalyst in the reaction mass. The latter method is preferred because it tends to make the resultant polymer more uniform in its chemical and physical properties.

Although the uniform distribution of the reactants throughout the reaction mass can be achieved by vigorous agitation, it is generally desirable to promote the uniform distribution of reagents by using inert wetting agents, or emulsion stabilizers. Suitable reagents for this purpose are the water-soluble salts of fatty acids, such as sodium oleate and potassium stearate, mixtures of water-soluble fatty acid salts, such as common soaps prepared by the saponification of animal and vegetable oils, the amino soaps, such as salts of triethanolamine and dodecylmethylamine, salts of rosin acids and mixtures thereof, the Water-soluble salts of half esters of sulfuric acid and long chain aliphatic alcohols, sulfonated hydrocarbons, such as alkyl aryl sulfonates, and any other of a Wide variety of wetting agents, which are in general organic compounds containing both hydrophobic and hydrophilic radicals. The quantity of emulsifying agents will depend upon the particular agents selected, the ratio of monomer to be used, and the conditions of polymerization. In general, however, from 0.01 to 1.0 percent by weight of the monomers may be employed.

The emulsion polymerizations are preferably conducted in glass or glass-lined vessels which are provided with a means for agitating the contents. Generally rotary stirring devices are the most effective means of insuring the intimate contact of the reagents, but other methods may be successfully employed, for example by rocking or tumbling the reactors. The polymerization equipment generally used is conventional in the art and the adaptation of a particular type of apparatus to the reaction contemplated is within the province of one skilled in the 'art. The articles manufactured therefrom may be produced by well-known conventional methods, forexample, the wet spinning, dry-spinning and melt-spinning methods for producing fibers.

The following examples are illustrative rather than limitative and all parts, proportions and percentages are by weight unless otherwise specified.

EXAMPLE I 7.5 grams of a polymer blend of 88 percent of a copolymer containing 94 percent of acrylonitrile and 6 percent of vinyl acetate and 12 percent of a copoly'nier of 50 percent of acrylonitrile and 50 percent of 2niethyl S-vinyl pyridine were added to-45 milliliters of N,N-

sav es dimethylacetamide containing approximately 0.05 gram of titanium dioxide. The mixture was stirred and heated to 70 C. It was then quickly cooled to roomtempera ture and the color measured. This sample was used as a control. The purity is set forth below. Subsequently, like samples were prepared but with 0.225 gram of a color inhibitor containing 0.075 gram each of sodium formaldehyde sulfoxylate, N-formyl morpholine and sulfuric acid; sodium formaldehyde sulfoxylate, N-formyl piperidine and sulfuric acid; sodium formaldehyde sulfoxylate, diformyl piperazine and sulfuric acid; and sodium formaldehyde sulfoxylate, N-formyl pyrrolidine and sulfuric acid. The purity is set forth below.

EXAMPLE II 7.5 grams of a copolymer containing 94 percent of acrylonitrile and 6 percent of vinyl acetate were added to 45 milliliters of N,N-dimethylacetamide containing approximately 0.05 gram of titanium dioxide. The mixture was stirred and heated for 35 minutes at 70 C. It was then quickly cooled to room temperature and the color measured. This sample was used as a control. The purity is set forth below. Subsequently, like samples were prepared but with 0.225 gram of an inhibiting agent containing 0.075 gram each of sodium formaldehyde sulfoxylate, N-formyl morpholine and sulfuric acid; sodium formaldehyde sulfoxylate, N-formyl piperidine and sulfuric acid; sodium formaldehyde sulfoxylate, diformyl piperazine and sulfuric acid; and sodium formaldehyde sulfoxylate, N-formyl pyrrolidine and sulfuric acid. The purity is set forth below.

EXAMPLE III 7.5 grams of an acrylonitrile homopolymer were added to 45 milliliters of N,N-dimethylacetamide containing approximately 005 gram of titanium dioxide. The mixture was stirred and heated for 50 minutes at 90 C. It was then quickly cooled to room temperature and the color measured. This sample was used as a control. The purity of the control sample is set forth below. Subsequently, like samples were prepared but with 0.225 gram of an inhibiting agent containing 0.075 gram each of sodium formaldehyde sulfoxylate, N-forrnyl morpholine and sulfuric acid; sodium formaldehyde sulfoxylate, N- formyl piperidine and sulfuric acid; sodium formaldehyde sulfoxylate, diformyl piperazine and sulfuric acid; 'and sodium' formaldehyde sulfoxylate, N-formyl pyrrolidine and sulfuric acid. The purity is set forthbelow. r15

The tests for color indicative of approaching whiteness used throughoutthe examples consist of measurements of purity as calculated from the tristirnulus values determined on a General Electric Spectrophotometer by the methods recommended by the Standard Observer and Coordinate System of the International Commisison on Illumination, as fully set forth in the Handbook of Colorimetry published by The Technology Press, Mas sachusetts Institute of Technology in 1936.

The compositions of the instant invention present many advantages. For example, products formed from the polymer solutions of the instant invention are free of objectionable color and therefore of greater commercial value. In preparing the polymer solutions, heat may be applied without the danger of color formation and the solutions, if necessary, may stand for prolonged periods and remain free of color. The inhibiting agents are readily available and inexpensive. Therefore, no great increase in production cost is necessary. The compositions containing the inhibitors may be prepared without going through detailed and elaborate procedures that necessitate expensive changes in the design of the apparatus used to manufacture them. 1

It will be understood to those skilled in the art that many apparently Widely different embodiments of this invention can be made without departing from the spirit and scope thereof. Accordingly, it is to be understood that this invention is not to be limited to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. A new composition of matter comprising a polymer containing at least percent of polymerized acrylonitrile and up to 20 percent of a mono-olefinic monomer copolymerizable therewith, a solvent therefor, and an inhibiting agent containing substantially equal proportions by weight of (I) a compound having the general formula,

CHr-CHz H N- =0 CHr-Cz wherein R is selected from the group consisting of oxygen and NCHO, and N-formyl pyrrolidine; and an inorganic acid having an ionization constant greater than l. 10-*.

2. A new composition of matter as defined in claim =1 wherein the polymer is a copolymer containing from'80 to 98 percent ofacrylonitrile and from.2-to. 20 percent :of

another polymerizable mono-olefinic monomer copolymerizable therewith.

3..- A new composition of matter as defined in claim 1 wherein the polymer is a blend of 80 to 99 percent of (A) a copolymer containing 90 to 98 percent of acrylonitrile and 2 to 10 percent of vinyl acetate and 1 to 20 percent of (B) a copolymer containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of 2-methyl-5-vinyl pyridine.

4. A new composition of matter as defined in claim 1 wherein the polymer is polyacrylonitrile.

' 5,. A new composition of matter as defined in claim 1 wherein compound (I) is sodium formaldehyde sulfoxylate.

6. A new composition of matter as defined in claim 1 wherein compound (I) is potassium formaldehyde sulfoxylate. I

7. A new composition of matter as defined in claim 1 wherein compound (I) is zinc formaldehyde sulfoxylate.

8. A new composition of matter as defined in claim 1 wherein compound (II) is N-formyl morpholine.

9. A new composition of matter as defined in claim 1 wherein compound (II) is N-formyl piperidine.

10. A new composition of matter as defined in claim 1 wherein, compound (II) is diformyl piperazine.

11. A new composition of matter as defined in claim 1 wherein compound (II) is N-formyl pyrrolidine.

12. A new composition of matter as defined in claim 1 wherein the solvent is N,N-dimethylacetamide.

13. A new composition of matter comprising a copolymer containing 80 to 98 percent of acrylonitrile and 2 to 20 percent of vinyl acetate, a solvent therefor, and 0.3 to 15 percent, based on the total Weight of the polymer, of. an inhibiting, agent, said inhibiting agent containing substantially equal proportions by weight of (I) a compound having the general formula,

l R O-M |n wherein R is a radical selected from the group consisting of alkanol groups containing 1 to 3 carbon atoms, having the free valence on a carbon atom attached to the hydroxyl group, n is an integer from 1 to 2, and M is a metal selected from the group consisting of sodium, potassiumand zinc; (II) a compound selected from the group of substances having the general formula,

wherein R is selected from the group consisting of 'JHn oxygen and NCHO, and N-formyl pyrrolidine; and sulfuric acid.

14. A new composition of matter comprising a polymer blend of 80 to 99 percent of (A) a copolymer containing 90 to 98 percent of acrylonitrile and 2 to percent of vinyl acetate and 1 to 20 percent of (B) a copolymer containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of 2-methyl-5-vinyl pyridine, a solvent therefor, and 0.3 to percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of (I) a compound having the general formula,

wherein R is a radical selected. from the group consisting of-alkanol groups containing 1 to. 3 carbon atoms, having the free valence on a carbon atom; attached to thethy- 8 droxyl group, n is an integer from 1 to 2, and M is. ametfl selected from the group consisting of sodium, potassium and zinc; (II) a compound selected from the group of substances having the general formula,

wherein R is selected from the group consisting of 3Hz oxygen and NCHO, and N-formyl pyrrolidine; and an furic acid.

15. A new composition of matter comprising polyacrylonitrile, a solvent therefor, and 0.3 to 15 percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing substantially equal proportions by weight of (I) a compound having the general formula,

fl s R O--M wherein R is a radical selected from the group consisting of alkanol groups containing 1 to 3 carbon atoms, having the free valence on a carbon atom attached to the hydroxyl group, n is an integer from 1 to 2, and M is a metal selected from the group consisting of sodium, potassium and zinc; (II) a compound selected from the group of substances having the general formula,

wherein R is selected from the group consisting of oxygen and NCHO, and N-formyl pyrrolidine; and sulfuric acid.

16. A method for preparing a new composition of matter comprising mixing a polymer containing at least percent of polymerized acrylonitrile and up to 20 per"- cent of a mono-olefinic monomer copolymerizable then with, a solvent therefor, and an inhibiting agent containing substantially equal proportions by weight of (I) a compound having the general formula,

wherein R is selected from group consisting of -(IJH: oxygen and NCHO, and N-formyl pyrrolidine; a'n'd inorganic acid having an ionization constant greater'th'an 1 10- and heating the mixture to form a homogeneous solution.

17. The method as defined in claim 16 wherein the polymer is a copolymer containing from 80 to 98 percent of acrylonitrile and from 2 to 2-0' percent of another polymerizable mono-olefinic monomer copolym'erizable therewith.

18. The method as defined in claim 16 wherein the polymer is a blend of 80 to 99 percent of (A) a copolymer containing 90 to 98 percent of acrylonitrile and 2 to percent of vinyl acetate and 1 to 20 percent of (B) a copolymer containing 10 to percent of acrylonitrile and 30 to 90 percent of 2-methyl-5-vinyl pyridine.

19. The method as defined in claim 16 wherein the polymer is polyacrylonitrile.

20. A method for preparing a new composition of matter comprising mixing a polymer blend of to 99 percent of (A) a copolymer containing to 98 percent of acrylonitrile and 2 to 10 percent of vinyl acetate and 1 to 20 percent of (B) a copolymer containing 10 to 70 percent of acrylonitrile and 30 to 90 percent of 2- methyl-S-vinyl pyridine, a solvent therefor, and 0.3 to 15 percent, based on the total weight of the polymer, of an inhibiting agent, said inhibiting agent containing sub- References Cited in the file of this patent UNITED STATES PATENTS 2,502,030 Scheiderbauer Mar. 28, 1950 2,560,694 Howard July 17, 1951 2,613,194 Craig Oct. 7, 1952 FOREIGN PATENTS 1,027,445 France May 12, 1953 UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,878,203 March 17, 1959 Richard R. Holmes et a].

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below. v

Column 3, line 59, for C= read C==C lines 71 and 72, for l-vinylimidazone read 1-viny1imidazole.

Signed and sealed this 4th day of August 1959.

Attest KARL H. AXLINE, ROBERT C. WATSON,

Attestz'ng Oficer. G'ommz'ssz'omr of Patents. 

1. A NEW COMPOSITION OF MATTER-COMPRISING A POLYMER CONTAINING AT LEAST 80 PERCENT OF POLYMERIZED ACRYLONITRILE AND UP TO 20 PERCENT OF A MONO-OLEFINIC MONOMER COPOLYMERIZABLE THEREWITH, A SOLVENT THEREFOR, AND AN INHIBITING AGENT CONTAINING SUBSTANTIALLY EQUAL PROPORTIONS BY WEIGHT OF (I) A COMPOUND HAVING THE GENERAL FORMULA 